TWI763760B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The invention relates to a liquid crystal alignment agent and a method for manufacturing the liquid crystal alignment agent. The liquid crystal alignment agent includes a polymer (A), a polysiloxane (B) and a solvent (C). The polymer (A) is formed by reacting a first mixture including a tetracarboxylic acid dianhydride component (a1) and a diamine component (a2), and is selected from a polyamide acid polymer, a polyimide polymer, a polyimide-based block copolymer or a combination thereof. The liquid crystal alignment agent of the invention has the advantages of favorable environmental resistance and adhesion strength. Furthermore, the invention also provides a liquid crystal alignment film made by the aforementioned liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film.

Description

Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

The present invention relates to a liquid crystal alignment agent and a method for producing the same, a liquid crystal alignment film and a method for producing the same, and a liquid crystal display element, and in particular, to a liquid crystal alignment agent with good environmental resistance and adhesion and a method for producing the same. A liquid crystal alignment film formed from a chemical agent, a method for producing the same, and a liquid crystal display element having the above-mentioned liquid crystal alignment film.

In general, in liquid crystal display elements, various driving methods have been developed depending on the electrode structure and the physical properties of liquid crystal molecules used. Currently known driving modes of liquid crystal display elements are, for example, TN type or STN type, VA type, lateral electric field effect display technology type (IPS type) and the like. The above-mentioned liquid crystal display element is provided with a liquid crystal alignment film in order to align liquid crystal molecules. The material of the liquid crystal alignment film can be, for example, known materials such as polyimide or polyimide, polyester, and polyorganosiloxane.

In recent years, new technologies such as Polymer Sustained Alignment (PSA) have been proposed in order to control the alignment of liquid crystal molecules in liquid crystal display elements, such as Japanese Publication No. JP 2003-149647, which describes the Polymer Sustained Alignment technology. The photopolymerizable component is added into the liquid crystal layer of the liquid crystal cell, and the liquid crystal molecules are tilted in the state of applying a voltage, and then the liquid crystal cell is irradiated with light to polymerize the photopolymerizable component, thereby controlling the alignment of the liquid crystal molecules. .

However, when using the polymer-stabilized alignment technology to control the alignment of liquid crystal molecules, a relatively high amount of light irradiation is required, resulting in defects such as decomposition of liquid crystal molecules and deterioration of the properties of the liquid crystal alignment film, resulting in display non-uniformity of the liquid crystal display element. And panel durability deteriorates. On the other hand, when the said light irradiation amount is reduced, the reaction speed of the liquid crystal molecules in the formed liquid crystal display element to a voltage change becomes slow. In order to make the liquid crystal alignment agent used for forming the coating film achieve a predetermined pretilt angle characteristic with a small amount of light irradiation as much as possible, and the liquid crystal molecules in the formed liquid crystal display element can respond quickly to voltage, it is currently proposed in Japanese Publication No. 2011 - The technology of the patent case No. 118358, which discloses the use of a liquid crystal alignment agent containing a photopolymerizable component such as a (meth)acryloyl group, a polyorganosiloxane, a polyimide or a polyimide, on a substrate. A liquid crystal alignment film is formed thereon. Next, the above-mentioned substrates were formed into liquid crystal cells, and when a voltage was applied between the substrates, the liquid crystal cells were irradiated with light to obtain a liquid crystal display element.

However, the liquid crystal alignment film and the liquid crystal display element prepared with the above-mentioned liquid crystal alignment agent still need to be improved in environmental resistance and adhesion. Therefore, there is an urgent need to provide a liquid crystal alignment agent, which can produce a liquid crystal alignment film and a liquid crystal display element with better environmental resistance and adhesion.

The present invention obtains a liquid crystal alignment agent by providing a special composition, and the liquid crystal alignment film and liquid crystal display element formed by the liquid crystal alignment agent have the advantages of good environmental resistance and adhesion.

式(1-1)至式(1-11)中，＊為鍵結處；及 該聚矽氧烷(B)包括由含環氧基的聚矽氧烷(b1)與側鏈化合物(b2)反應所製得，且該含環氧基的聚矽氧烷(b1)包含由一第二混合物經加水分解及部份縮合而得之共聚物。Therefore, the present invention relates to a liquid crystal aligning agent, comprising: a polymer (A) prepared by reacting a first mixture comprising a tetracarboxylic dianhydride component (a1) and a diamine component (a2). , and the polymer (A) is selected from polyimide polymer, polyimide polymer, polyimide block copolymer or any combination of the above polymers; polysiloxane (B) and solvent (C); wherein the diamine component (a2) comprises at least one first diamine compound (a2-1) represented by formula (1): H ₂ N—R _a —NH ₂ formula (1) In formula (1), R _a is a divalent unit represented by formula (1-1) to formula (1-11):

In formula (1-1) to formula (1-11), * is a bond; and the polysiloxane (B) includes an epoxy group-containing polysiloxane (b1) and a side chain compound (b2) ) reaction, and the epoxy-containing polysiloxane (b1) comprises a copolymer obtained by hydrolysis and partial condensation of a second mixture.

The present invention further provides a liquid crystal alignment film, which is formed by the aforementioned liquid crystal alignment agent.

The present invention also provides a liquid crystal display element comprising the aforementioned liquid crystal alignment film.

式(1-1)至式(1-11)中，＊為鍵結處；及 該聚矽氧烷(B)包括由含環氧基的聚矽氧烷(b1)與側鏈化合物(b2)反應所製得，且該含環氧基的聚矽氧烷(b1)包含由一第二混合物經加水分解及部份縮合而得之共聚物。The present invention provides a liquid crystal alignment agent, comprising: a polymer (A) prepared by reacting a first mixture including a tetracarboxylic dianhydride component (a1) and a diamine component (a2), and the The polymer (A) is selected from the group consisting of a polyimide polymer, a polyimide polymer, a polyimide-based block copolymer or any combination of the foregoing polymers; a polysiloxane (B); and a solvent (C); wherein the diamine component (a1) includes at least one first diamine compound (a2-1) represented by the formula (1): H ₂ N—R _a —NH ₂ Formula (1) Formula (1) ), R _a is a divalent unit represented by formula (1-1) to formula (1-11):

In formula (1-1) to formula (1-11), * is a bond; and the polysiloxane (B) includes an epoxy group-containing polysiloxane (b1) and a side chain compound (b2) ) reaction, and the epoxy-containing polysiloxane (b1) comprises a copolymer obtained by hydrolysis and partial condensation of a second mixture.

The polymer (A) according to the present invention is obtained by reacting a first mixture comprising a tetracarboxylic dianhydride component (a1) and a diamine component (a2).

Specifically, the polymer (A) is selected from the group consisting of a polyimide polymer, a polyimide polymer, a polyimide-based block copolymer, and any combination of the aforementioned polymers. Preferably, the polymer (A) is a combination of a polyimide polymer (A1) and a polyimide polymer (A2).

In a specific example of the present invention, based on 100 parts by weight of the polymer (A), the amount of the polyamide polymer (A1) used is 20 to 60 parts by weight, preferably 25 parts by weight parts to 60 parts by weight, more preferably 25 parts to 55 parts by weight; and the amount of the polyimide polymer (A2) used is 40 parts to 80 parts by weight, preferably 40 parts to 75 parts by weight , more preferably 45 to 75 parts by weight. If the usage amounts of the polyimide polymer (A1) and the polyimide polymer (A2) both fall within the above ranges, the obtained liquid crystal aligning agent has the best environmental resistance and adhesion .

The tetracarboxylic dianhydride compound (a1) includes aliphatic tetracarboxylic dianhydride compounds, alicyclic tetracarboxylic dianhydride compounds, aromatic tetracarboxylic dianhydride compounds, from formula (I-1) to formula (I) -6) At least one of the tetracarboxylic dianhydride compounds represented, or a combination of the above compounds.

Specific examples of the aliphatic tetracarboxylic dianhydride compound, the alicyclic tetracarboxylic dianhydride compound, and the aromatic tetracarboxylic dianhydride compound are listed below, but the present invention is not limited to these specific examples.

Specific examples of the aliphatic tetracarboxylic dianhydride compound may include, but are not limited to, ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, or a combination of the above compounds.

Specific examples of the alicyclic tetracarboxylic dianhydride compound may include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclo Butanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl Cycloheptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, or a combination of the foregoing.

Specific examples of the aromatic tetracarboxylic dianhydride compound may include, but are not limited to, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid Acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-diphenylethane tetracarboxylic dianhydride, 3,3',4,4'- Dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylene dianhydride, 4,4'- 4,4'-bis(3,4-dicarboxy phenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisosulfite Propyl diphthalic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(tris) Phenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid) dianhydride (Triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(anhydrotrimellitate), propylene glycol-bis(anhydrotrimellitate), 1,4 -Butanediol-bis(anhydrotrimellitate), 1,6-hexanediol-bis(anhydrotrimellitate), 1,8-octanediol-bis(anhydrotrimellitate) , 2,2-bis(4-hydroxyphenyl)propane-bis(anhydro trimellitate), 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5, 9b-Hexahydro-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione{(1,3, 3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione)}, 1,3,3a,4 ,5,9b-Hexahydro-5-methyl-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1,2-c]-furan-1,3- Diketone, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1,2 -c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxy-3- Furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2 ,5-Di-oxy-3-furyl)-naphtho[ 1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxyl -3-Furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrakis Hydro-2,5-di-oxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro -5,8-Dimethyl-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 5 Aromatic tetracarboxylic dianhydride compounds such as -(2,5-dioxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, or a combination of the above-mentioned compounds.

式(I-1)

式(I-2)

式(I-3)

式(I-4)

式(I-5)The tetracarboxylic dianhydride compounds represented by formula (I-1) to formula (I-6) are shown below.

Formula (I-1)

Formula (I-2)

Formula (I-3)

Formula (I-4)

Formula (I-5)

式(I-5-1)

式(I-5-2)

式(I-5-3)

式(I-6)In formula (I-5), A ¹ represents a divalent group containing an aromatic ring; r represents an integer of 1 to 2; A ² and A ³ may be the same or different, and may each independently represent a hydrogen atom or an alkyl group. Specific examples of the tetracarboxylic dianhydride compound represented by the formula (I-5) include at least one of the compounds represented by the formula (I-5-1) to the formula (I-5-3).

Formula (I-5-1)

Formula (I-5-2)

Formula (I-5-3)

Formula (I-6)

式(I-6-1)In formula (I-6), A ⁴ represents a divalent group containing an aromatic ring; A ⁵ and A ⁶ may be the same or different, and each independently represents a hydrogen atom or an alkyl group. The tetracarboxylic dianhydride compound represented by the formula (I-6) is preferably a compound represented by the formula (I-6-1).

Formula (I-6-1)

The tetracarboxylic dianhydride compound (a1) may be used alone or in combination of two or more.

Specific examples of the tetracarboxylic dianhydride compound (a1) preferably include 1,2,3,4-cyclobutane tetracarboxylic dianhydride (1,2,3,4-cyclobutane tetracarboxylic dianhydride), 1,2, 3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride (2,3,5-tricarboxycyclopentylacetic dianhydride), 1,2,4,5-cyclohexanetetrakis Carboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3',4, 4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, a compound represented by formula (I-1), or a combination of the above compounds.

Based on the total molar number of the diamine component (a2) being 100 moles, the usage amount of the tetracarboxylic dianhydride component (a1) is preferably in the range of 80 moles to 120 moles, more preferably 85 moles to 115 moles.

式(1-1)至式(1-11)中，＊為鍵結處；及The diamine component (a2) according to the present invention includes at least one first diamine compound (a2-1) represented by the formula (1): H ₂ N—R _a —NH ₂ in the formula (1) in the formula (1) , R _a is a divalent unit represented by formula (1-1) to formula (1-11):

In formula (1-1) to formula (1-11), * is the bond; and

In a specific example of the present invention, based on the total usage amount of the diamine component (a2) is 100 moles, the usage amount of the first diamine compound (a2-1) represented by the formula (1) is 3 to 100 moles. 60 moles, preferably 5 to 50 moles, more preferably 8 to 40 moles. If the first diamine compound (a2-1) is not used, the obtained liquid crystal aligning agent will have poor environmental resistance and poor adhesion.

式(2) 式(2)中，R¹⁵ 為選自由

、

、

、

、

及

所組成之群；及 R¹⁶ 為式(2-1)所示之有機基團：

式(2-1) 式(2-1)中： R¹⁷ 為氫、氟或甲基； R¹⁸ 、R¹⁹ 及R²⁰ 各自獨立地表示單鍵、

、

、

、

、

、

或C₁ 至C₃ 的伸烷基； R²¹ 係選自由

及

所組成之群； 其中： R²³ 及R²⁴ 各自獨立地表示氫、氟或甲基； R²² 係選自由氫、氟、C₁ 至C₁₂ 的烷基、C₁ 至C₁₂ 的氟烷基、C₁ 至C₁₂ 的烷氧基、-OCH₂ F、-OCHF₂ 及-OCF₃ 所組成之群； a表示1或2的整數； g、m及i各自獨立地表示0至4的整數； y、h及x各自獨立地表示0至3的整數，且y+h+x≧3；及 z1及z2各自獨立地表示1或2； 當R¹⁷ 、R¹⁸ 、R¹⁹ 、R²⁰ 、R²¹ 、R²³ 或R²⁴ 為多個時，其各自為相同或不同。Preferably, the diamine component (a2) of the present invention may further comprise the second diamine compound (a2-2) represented by the formula (2):

Formula (2) In formula (2), R ¹⁵ is selected from

,

,

,

,

and

and R ¹⁶ is an organic group represented by formula (2-1):

Formula (2-1) In formula (2-1): R ¹⁷ is hydrogen, fluorine or methyl; R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a single bond,

,

,

,

,

,

or C ₁ to C ₃ alkylene; R ²¹ is selected from

and

The group consisting of; wherein: R ²³ and R ²⁴ independently represent hydrogen, fluorine or methyl; R ²² is selected from hydrogen, fluorine, C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ fluoroalkyl , C ₁ to C ₁₂ alkoxy group, -OCH ₂ F, -OCHF ₂ and -OCF ₃ ; a represents an integer of 1 or 2; g, m and i each independently represent an integer of 0 to 4 ; y, h and x each independently represent an integer from 0 to 3, and y+h+x≧3; and z1 and z2 each independently represent 1 or 2; when R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , When there are more than one R ²¹ , R ²³ or R ²⁴ , they are the same or different from each other.

式(2-2)

式(2-3)

式(2-4)

式(2-5)

式(2-6)

式(2-7)

式(2-8)

式(2-9) 式(2-2)至式(2-9)中，B¹¹ 為氫原子、碳數為1至10的烷基或碳數為1至10的烷氧基。Specific examples of the second diamine compound (a2-2) include at least one of the diamine compounds represented by formula (2-2) to formula (2-9), or a combination of the above compounds.

Formula (2-2)

Formula (2-3)

Formula (2-4)

Formula (2-5)

Formula (2-6)

Formula (2-7)

Formula (2-8)

Formula (2-9) In formula (2-2) to formula (2-9), B ¹¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

式(2-10)

式(2-11)

式(2-12)

式(2-13)

式(2-14)

式(2-15)The diamine compound represented by the formula (2-2) to the formula (2-9) is preferably at least one of the diamine compounds represented by the formula (2-10) to the formula (2-15), or the above compounds. combination.

Formula (2-10)

Formula (2-11)

Formula (2-12)

Formula (2-13)

Formula (2-14)

Formula (2-15)

The above-mentioned second diamine compound (a2-2) may be used alone or in combination of two or more.

In a specific example of the present invention, based on the total usage amount of the diamine component (a2) is 100 moles, the usage amount of the second diamine compound (a2-2) represented by the formula (2) is 5 to 100 moles. 60 moles, preferably 8 to 50 moles, more preferably 10 to 40 moles.

式(3) 式(3)中，X為含C₆ 至C₃₀ 芳香環之有機基；及 n為1至4之整數。Preferably, the diamine component (a2) of the present invention may further comprise the third diamine compound (a2-3) represented by the formula (3):

Formula (3) In formula (3), X is an organic group containing a C ₆ to C ₃₀ aromatic ring; and n is an integer of 1 to 4.

The structure of the third diamine compound (a2-3) is not particularly limited as long as it has a carboxylic acid group, and the third diamine compound (a2-3) may include, but is not limited to, aliphatic diamine, alicyclic diamines, aromatic diamines or diamine-based organosiloxanes. The third diamine compound (a2-3) is preferably an alicyclic diamine or an aromatic diamine, more preferably an aromatic diamine.

The third diamine compound (a2-3) preferably has 1 to 4 carboxylic acid groups, and more preferably has 1 or 2 carboxylic acid groups.

式(3-1)

式(3-2)

式(3-3)

式(3-4)

式(3-5) 式(3-1)至式(3-5)中，X₁ 及X₃ 獨立地表示單鍵、-CH₂ -、-C₂ H₄ -、-C(CH₃ )₂ -、-CF₂ -、-C(CF₃ )₂ -、-O-、-CO-、-NH-、-N(CH₃ )-、-CONH-、-NHCO-、-CH₂ O-、-OCH₂ -、-COO-、-OCO-、-CON(CH₃ )-或-N(CH₃ )CO-； X₂ 表示C₁ 至C₅ 之直鏈烷基或C₁ 至C₅ 之支鏈烷基； n1及n7獨立地表示1至4之整數； n2及n3獨立地表示0至4之整數，且n2＋n3為1至4之整數；及 n4、n5及n6獨立地表示1至5之整數。The third diamine compound (a2-3) is selected from the group consisting of formula (3-1) to formula (3-5);

Formula (3-1)

Formula (3-2)

Formula (3-3)

Formula (3-4)

Formula (3-5) In formula (3-1) to formula (3-5), X ₁ and X ₃ independently represent a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O- , -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-; X ₂ represents C ₁ to C ₅ straight chain alkyl or C ₁ to C ₅ n1 and n7 independently represent an integer from 1 to 4; n2 and n3 independently represent an integer from 0 to 4, and n2+n3 independently represent an integer from 1 to 4; and n4, n5, and n6 independently represent an integer from 1 to 4 An integer of 5.

Preferably, in formula (3-1), n1 can represent 1 or 2; in formula (3-2), X ₁ represents a single bond, -CH ₂ -, -C ₂ H ₄ -, -C ( CH ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO- or -OCO-, and n2 and n3 represent 1 at the same time; In formula (3-5), X ₃ represents a single bond, -CH ₂ -, -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ - , -COO- or -OCO-, and n7 represents 1 or 2.

於式(3-14)及式(3-15)中，X₅ 可代表單鍵、-CH₂ -、-O-、-CO-、-NH-、-CONH-、-NHCO-、-CH₂ O-、-OCH₂ -、-COO-或-OCO-。Specific examples of the third diamine compound (a2-3) are the diamine compounds represented by the following formulae (3-6) to (3-16):

In formula (3-14) and formula (3-15), X ₅ can represent a single bond, -CH ₂ -, -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-.

The aforementioned third diamine compound (a2-3) may be used alone or in combination of two or more.

In a specific example of the present invention, based on the total usage amount of the diamine component (a2) is 100 moles, the usage amount of the third diamine compound (a2-3) represented by the formula (3) is 3 to 100 moles. 97 moles, preferably 5 to 90 moles, more preferably 10 to 80 moles. When the second diamine compound (a2-2) or the third diamine compound (a2-3) is used, the obtained liquid crystal aligning agent has better environmental resistance.

Preferably, the diamine component (a2) of the present invention may further comprise other diamine compounds (a2-4).

The other diamine compound (a2-4) may include, but is not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diamine pentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diamine decane, 4,4'-diaminoheptane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane , 1,9-diamino-5-methylnonane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis(3-aminopropoxy yl)ethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1,3-diaminocyclohexane , 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, tricyclic (6.2.1.0 ^2,7 )-undecene dimethyl diamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4' -Diaminodiphenyl ether, 4,4'-diaminobenzylaniline, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1, 5-Diaminonaphthalene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydroindene, 6-amino-1-(4'-aminobenzene) base)-1,3,3-trimethylhydroindene, hexahydro-4,7-methylhydroindenyl dimethylenediamine, 3,3'-diaminobenzophenone, 3, 4'-Diaminobenzophenone, 4,4'-Diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2- Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-amino) Phenoxy)phenyl] benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-amine phenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 9,10-bis(4-aminophenyl)anthracene [9,10-bis(4-aminophenyl) ) anthracene], 2,7-diamino fluoride, 9,9-bis(4-aminophenyl) fluoride, 4,4'-methylene-bis(2-chloroaniline), 4,4'- (p-phenylene isopropylidene) bisaniline, 4,4'-(m-phenylene isopropylidene) bisaniline, 2,2'-bis[4-(4-amino-2- Trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 5-[4- (4-n-Pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene{5-[4-(4-n-pentylcyc lohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene}, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane{1, 1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane} or other diamine compounds represented by the following formulae (4-1) to (4-25).

式(4-1) 於式(4-1)中，X₆ 代表

、

、

、

、

或

，且X₇ 代表含甾基團、三氟甲基、氟基、碳數為2至30之烷基或衍生自吡啶、嘧啶、三嗪、哌啶及哌嗪等含氮原子環狀結構的一價基團。The diamine compound represented by formula (4-1) is shown below:

Formula (4-1) In formula (4-1), X ₆ represents

,

,

,

,

or

, and X ₇ represents a steroid group, a trifluoromethyl group, a fluoro group, an alkyl group with a carbon number of 2 to 30, or a nitrogen atom-containing cyclic structure derived from pyridine, pyrimidine, triazine, piperidine and piperazine. monovalent group.

式(4-1-1)

式(4-1-2)

式(4-1-3)

式(4-1-4)

式(4-1-5)

式(4-1-6)The other diamine compound (a2-4) represented by the above formula (4-1) is preferably 2,4-diaminophenyl ethyl formate, 3,5-diamine 3,5-diaminophenyl ethyl formate, 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate (3,5-diaminophenyl propyl formate), 1-dodecoxy-2,4-diaminobenzene (1-dodecoxy-2,4-diaminobenzene), 1-hexadecoxy-2,4- Diaminobenzene (1-hexadecoxy-2,4-diaminobenzene), 1-octadecoxy-2,4-diaminobenzene (1-octadecoxy-2,4-diaminobenzene) or the following formula (4-1 -1) to other diamine compounds represented by formula (4-1-6):

Formula (4-1-1)

Formula (4-1-2)

Formula (4-1-3)

Formula (4-1-4)

Formula (4-1-5)

Formula (4-1-6)

式(4-2) 於式(4-2)中，X₈ 代表

、

、

、

、

或

，X₉ 及X₁₀ 表示伸脂肪族環、伸芳香族環或伸雜環基團，且X₁₁ 代表碳數為3至18之烷基、碳數為3至18之烷氧基、碳數為1至5之氟烷基、碳數為1至5之氟烷氧基、氰基或鹵素原子。The diamine compound represented by the formula (4-2) is shown below:

Formula (4-2) In formula (4-2), X ₈ represents

,

,

,

,

or

, X ₉ and X ₁₀ represent extended aliphatic ring, extended aromatic ring or extended heterocyclic group, and X ₁₁ represents an alkyl group with a carbon number of 3 to 18, an alkoxy group with a carbon number of 3 to 18, a carbon number is a fluoroalkyl group of 1 to 5, a fluoroalkoxy group having a carbon number of 1 to 5, a cyano group or a halogen atom.

式(4-2-1)

式(4-2-2)

式(4-2-9)

式(4-2-10)

式(4-2-11)

式(4-2-12)

式(4-2-13) 於式(4-2-10)至式(4-2-13)中，s可代表3至12之整數。The other diamine compounds (a2-4) represented by the above formula (4-2) are preferably diamine compounds represented by the following formulas (4-2-1) to (4-2-13):

Formula (4-2-1)

Formula (4-2-2)

Formula (4-2-9)

Formula (4-2-10)

Formula (4-2-11)

Formula (4-2-12)

Formula (4-2-13) In Formula (4-2-10) to Formula (4-2-13), s may represent an integer of 3 to 12.

式(4-3) 於式(4-3)中，X₁₂ 代表氫原子、碳數為1至5的醯基、碳數為1至5的烷基、碳數為1至5的烷氧基或鹵素，且每個重複單元中的X₁₂ 可為相同或不同。X₁₃ 為1至3的整數。The diamine compound represented by the formula (4-3) is shown below:

Formula (4-3) In formula (4-3), X ₁₂ represents a hydrogen atom, an acyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. group or halogen, and X ₁₂ in each repeating unit may be the same or different. X ₁₃ is an integer of 1 to 3.

The diamine compound represented by the formula (4-3) is preferably selected from (1) X ₁₃ is 1: p-diamine benzene, m-diamine benzene, o-diamine benzene or 2,5-diamine Amine toluene, etc.; (2) X ₁₃ is 2:4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethylbenzene Alkyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino Biphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl or 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, etc.; (3) X ₁₃ is 3:1,4-bis(4'-aminophenyl)benzene, etc., more preferably selected from p-diaminebenzene, 2,5-diaminetoluene, 4,4'- Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl or 1,4-bis(4'-aminophenyl)benzene.

式(4-4) 於式(4-4)中，X₁₄ 代表2至12的整數。The diamine compound represented by formula (4-4) is shown below:

Formula (4-4) In Formula (4-4), X ₁₄ represents an integer of 2 to 12.

式(4-5) 於式(4-5)中，X₁₅ 代表1至5之整數。該式(4-5)較佳係選自於4,4’-二胺基二苯基硫醚。The diamine compound represented by formula (4-5) is shown below:

Formula (4-5) In Formula (4-5), X ₁₅ represents an integer of 1 to 5. The formula (4-5) is preferably selected from 4,4'-diaminodiphenyl sulfide.

式(4-6) 於式(4-6)中，X₁₆ 及X₁₈ 可為相同或不同，且分別代表二價有機基團，X₁₇ 代表衍生自吡啶、嘧啶、三嗪、哌啶及哌嗪等含氮原子環狀結構的二價基團。The diamine compound represented by the formula (4-6) is shown below:

Formula (4-6) In formula (4-6), X ₁₆ and X ₁₈ may be the same or different, and respectively represent a divalent organic group, X ₁₇ represents a group derived from pyridine, pyrimidine, triazine, piperidine and Piperazine and other divalent groups of nitrogen-containing cyclic structures.

式(4-7) 於式(4-7)中，X₁₉ 、X₂₀ 、X₂₁ 及X₂₂ 分別可為相同或不同，且可代表碳數為1至12的烴基。X₂₃ 代表1至3之整數，且X₂₄ 代表1至20之整數。The diamine compound represented by the formula (4-7) is shown below:

Formula (4-7) In formula (4-7), X ₁₉ , X ₂₀ , X ₂₁ and X ₂₂ may be the same or different, respectively, and may represent a hydrocarbon group having 1 to 12 carbons. X ₂₃ represents an integer from 1 to 3, and X ₂₄ represents an integer from 1 to 20.

式(4-8) 於式(4-8)中，X₂₅ 代表

或伸環己烷基，X₂₆ 代表-CH₂ -，X₂₇ 代表伸苯基或伸環己烷基，且X₂₈ 代表氫原子或庚基。The diamine compound represented by the formula (4-8) is shown below:

Formula (4-8) In formula (4-8), X ₂₅ represents

or a cyclohexylene group, X ₂₆ represents -CH ₂ -, X ₂₇ represents a phenylene group or a cyclohexylene group, and X ₂₈ represents a hydrogen atom or a heptyl group.

式(4-8-1)

式(4-8-2)The diamine compound represented by the formula (4-8) is preferably selected from the diamine compounds represented by the following formulas (4-8-1) to (4-8-2):

Formula (4-8-1)

Formula (4-8-2)

式(4-9)

式(4-10)

式(4-11)

式(4-12)

式(4-13)

式(4-14)

式(4-15)

式(4-16)

式(4-21)

式(4-22)

式(4-23)

式(4-24)

式(4-25) 於式(4-17)至式(4-25)中，X₂₉ 以碳數為1至10之烷基，或著碳數為1至10之烷氧基為較佳，而X₃₀ 以氫原子、碳數為1至10之烷基或碳數為1至10之烷氧基為較佳。Other diamine compounds represented by formula (4-9) to formula (4-25) are as follows:

Formula (4-9)

Formula (4-10)

Formula (4-11)

Formula (4-12)

Formula (4-13)

Formula (4-14)

Formula (4-15)

Formula (4-16)

Formula (4-21)

Formula (4-22)

Formula (4-23)

Formula (4-24)

Formula (4-25) In formula (4-17) to formula (4-25), X ₂₉ is preferably an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. , and X ₃₀ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

The other diamine compound (a2-4) may preferably include but not limited to 1,2-diaminoethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl ether, 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene, 1 ,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane, ethyl 2,4-diaminophenylcarboxylate, formula (4 -1-1), formula (4-1-2), formula (4-1-5), formula (4-1-6), formula (4-2-1), formula (4-2-11) , p-diamine benzene, m-diamine benzene, o-diamine benzene, a compound represented by formula (4-8-1).

The aforementioned other diamine compounds (a2-4) may be used alone or in combination.

In a specific example of the present invention, based on the total usage amount of the diamine component (a2) is 100 moles, the usage amount of the other diamine compounds (a2-4) is 0 to 97 moles, preferably 0 to 97 moles. 90 moles, more preferably 0 to 80 moles. [ Production method of polymer (A) ]

The polymer (A) may include at least one of a polyimide polymer (A1) and a polyimide polymer (A2). In addition, the polymer (A) may further include a polyimide-based block copolymer. The preparation methods of the above-mentioned various polymers are further described below. <Preparation method of polyamide polymer (A1)>

The method for preparing the polyamic acid polymer (A1) is to first dissolve the first mixture in a solvent, wherein the first mixture includes the tetracarboxylic dianhydride component (a1) and the diamine component (a2), The polycondensation reaction is carried out at a temperature of 0°C to 100°C. After 1 hour to 24 hours of reaction, the reaction solution is distilled under reduced pressure with an evaporator to obtain polyamic acid. Alternatively, the reaction solution is poured into a large amount of lean solvent to obtain a precipitate. Next, the precipitate is dried under reduced pressure to obtain a polyamide acid.

The solvent used in the polycondensation reaction may be the same as or different from the solvent used in the liquid crystal aligning agent described below, and the solvent used in the polycondensation reaction is not particularly limited as long as it can dissolve the reactant and the product. The solvent preferably includes but is not limited to (1) aprotic polar solvents, such as: N-methyl-2-pyrrolidinone (N-methyl-2-pyrrolidinone; NMP), N,N-dimethylacetamide, Aprotic polar solvents such as N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea or hexamethylphosphoric triamine; or (2) phenolic solvents, For example, phenolic solvents such as m-cresol, xylenol, phenol, and halogenated phenols. The used amount of the solvent used in the polycondensation reaction is preferably 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight, based on 100 parts by weight of the total used amount of the first mixture.

It is worth noting that in the polycondensation reaction, the solvent can be used in combination with an appropriate amount of poor solvent, wherein the poor solvent will not cause the precipitation of polyamide acid. The poor solvent can be used alone or in combination, and it includes but is not limited to (1) alcohols, such as methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol Alcohols such as alcohol or triethylene glycol; (2) ketones, such as: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; (3) esters, such as: Esters of methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate or ethylene glycol ethyl ether acetate; (4) ethers, such as diethyl ether, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether ethers such as base ethers; (5) halogenated hydrocarbons, such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene or o-dichloromethane Halogenated hydrocarbons such as benzene; or (6) hydrocarbons, for example: hydrocarbons such as tetrahydrofuran, hexane, heptane, octane, benzene, toluene or xylene, or any combination of the above solvents. Based on 100 parts by weight of the diamine component (a2), the amount of the lean solvent is preferably 0 to 60 parts by weight, and more preferably 0 to 50 parts by weight.

The weight average molecular weight of the polyamic acid polymer (A1) is 30,000 to 200,000; preferably 30,000 to 180,000; more preferably 30,000 to 150,000. <Method for producing polyimide polymer (A2)>

The method for preparing the polyimide polymer (A2) is obtained by heating the polyamic acid prepared by the above-mentioned method for preparing polyamic acid in the presence of a dehydrating agent and a catalyst. During the heating process, the aramidic acid functional group in the polyamic acid can be converted into an imidimine functional group via a dehydration ring-closure reaction (ie, imidization).

The solvent used in the dehydration ring-closing reaction can be the same as the solvent (C) in the liquid crystal alignment agent, so it is not repeated here. The amount of the solvent used in the dehydration ring-closure reaction is preferably 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight, based on 100 parts by weight of the polyamic acid.

In order to obtain a better degree of imidization of the polyamic acid, the operating temperature of the dehydration ring-closure reaction is preferably 40°C to 200°C, more preferably 40°C to 150°C. If the operating temperature of the dehydration ring-closure reaction is lower than 40° C., the imidization reaction is incomplete, and the degree of imidization of the polyamic acid is reduced. However, if the operating temperature of the dehydration ring-closure reaction is higher than 200°C, the weight-average molecular weight of the obtained polyimide is relatively low.

The dehydrating agent used in the dehydration ring-closure reaction can be selected from acid anhydride compounds, such as acid anhydride compounds such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The dehydrating agent is used in an amount of 0.01 mol to 20 mol based on 1 mol of the polyamide. The catalyst used in the dehydration ring-closure reaction can be selected from (1) pyridine compounds, such as: pyridine compounds such as pyridine, collidine or lutidine; (2) tertiary amine compounds, such as: Tertiary amine compounds such as triethylamine. The catalyst may be used in an amount of 0.5 mol to 10 mol based on 1 mol of the dehydrating agent.

The weight average molecular weight of the polyimide polymer (A2) is 30,000 to 200,000; preferably 30,000 to 180,000; more preferably 30,000 to 150,000.

The imidization rate of the polymer (A) may be 30% to 80%, preferably 35% to 80%, and more preferably 35% to 75%. If the imidization rate of the polymer (A) is within the above range, the adhesiveness of the obtained liquid crystal aligning agent is better. <Method for producing polyimide-based block copolymer>

The polyimide block copolymer is selected from the group consisting of polyimide block copolymer, polyimide block copolymer, polyimide-polyimide block copolymer or the above-mentioned polymerization any combination of things.

The method for preparing the polyimide-based block copolymer is preferably to first dissolve the starting material in a solvent and carry out a polycondensation reaction, wherein the starting material includes at least one polyamide acid and/or at least one polyamide imine, and may further include a carboxylic acid anhydride component and a diamine component.

The carboxylic acid anhydride component and the diamine component in the starting material can be the same as the tetracarboxylic dianhydride component (a1) and the diamine component (a2) used in the method for preparing polyamic acid, and are used for The solvent in the polycondensation reaction can be the same as the solvent (C) in the following liquid crystal alignment agent, and details are not described here.

The solvent used in the polycondensation reaction is preferably used in an amount of 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight, based on 100 parts by weight of the starting material. The operating temperature of the polycondensation reaction is preferably 0°C to 200°C, and more preferably 0°C to 100°C.

The starting materials preferably include but are not limited to (1) two kinds of polyamides with different end groups and different structures; (2) two kinds of polyimides with different end groups and different structures; (3) ) Polyamides and polyimides with different terminal groups and different structures; (4) Polyamides, carboxylic anhydride components and diamine components, wherein the difference between the carboxylic acid anhydride component and the diamine component At least one of the structures is different from the carboxylic acid anhydride component and the diamine component used to form the polyamide acid; (5) the polyimide, the carboxylic acid anhydride component and the diamine component, wherein, the carboxylic acid anhydride component At least one of the components and the diamine component is different in structure from the carboxylic acid anhydride component and the diamine component used to form the polyimide; (6) polyamide acid, polyimide, and carboxylic acid anhydride components and the diamine component, wherein at least one of the carboxylic acid anhydride component and the diamine component has a different structure from the carboxylic acid anhydride component and the diamine component used to form the polyamide acid or polyimide; ( 7) Two kinds of structurally different polyamide acids, carboxylic anhydride components and diamine components; (8) Two kinds of structurally different polyimide, carboxylic acid anhydride components and diamine components; (9) Two kinds of end groups are acid anhydride groups and structurally different polyamic acid and diamine components; (10) Two kinds of end groups are amine groups and structurally different polyamic acid and carboxylic anhydride components; (11) Two kinds of end groups are polyimide and diamine components with different structures and acid anhydride groups; or (12) two kinds of polyimide and carboxylic acid anhydride components with amine groups and different structures.

In the range that does not affect the efficacy of the present invention, polyimide, polyimide and polyimide-based block copolymers are preferably terminal-modified polymers whose molecular weights are adjusted first. By using the terminal-modified polymer, the coating performance of the liquid crystal alignment agent can be improved. The method of preparing the terminal-modified polymer can be prepared by adding a monofunctional compound at the same time as the polyamide acid undergoes a polycondensation reaction.

Specific examples of monofunctional compounds include, but are not limited to (1) monobasic acid anhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride Monobasic acid anhydrides such as alkyl succinic anhydride or n-hexadecyl succinic anhydride; (2) monoamine compounds, such as: aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, Monoamine compounds such as n-octadecylamine or n-eicosylamine; or (3) monoisocyanate compounds, for example: monoisocyanate compounds such as phenyl isocyanate or naphthyl isocyanate.

The polysiloxane (B) is prepared by reacting an epoxy group-containing polysiloxane (b1) with a side chain compound (b2), and the epoxy group-containing polysiloxane (b1) includes a A copolymer obtained by hydrolysis and partial condensation of the second mixture.

wherein the epoxy group-containing polysiloxane (b1) contains at least one of the group represented by the formula (III-1), the group represented by the formula (III-2), and the group represented by the formula (III-3) one.

式(III-1)Specifically, the group represented by formula (III-1) is shown below.

Formula (III-1)

In formula (III-1), B represents an oxygen atom or a single bond; c represents an integer of 1 to 3; d represents an integer of 0 to 6, wherein when d represents 0, B is a single bond.

式(III-2)In addition, the group represented by the formula (III-2) is shown below.

Formula (III-2)

In formula (III-2), e represents an integer of 0 to 6.

式(III-3)The group represented by formula (III-3) is shown below.

Formula (III-3)

In formula (III-3), D represents a C ₂ to C ₆ alkylene group; E represents a hydrogen atom or a C ₁ to C ₆ alkyl group.

式(III-1-1)

式(III-2-1)

式(III-3-1)The epoxy group-containing group preferably includes a group represented by formula (III-1-1), a group represented by formula (III-2-1), and a group represented by formula (III-3-1) at least one of.

Formula (III-1-1)

Formula (III-2-1)

Formula (III-3-1)

The epoxy-containing polysiloxane (b1) of the present invention comprises a copolymer obtained by hydrolysis and partial condensation of a second mixture comprising a silane monolayer represented by formula (III-4) body (b1-1); Si(R _f ) _b (OR _g ) _4-b formula (III-4) In formula (III-4), R _f is a hydrogen atom, an alkyl group of C ₁ to C ₁₀ , C ₂ to _C10 alkenyl, _C6 to _C15 aryl, epoxy-containing alkyl or epoxy-containing alkoxy, and at least one R _f is epoxy-containing alkyl or ring-containing Alkoxy of oxy; When b is plural, R _f are each the same or different; R _g is hydrogen atom, C ₁ to C ₆ alkyl group, C ₁ to C ₆ aryl group or C ₆ to C ₁₅ aryl; when 4-b is plural, each of R _g is the same or different; and b is an integer of 1 to 3.

In more detail, when R _f in formula (III-4) represents a C ₁ to C ₁₀ alkyl group, specifically, R _f is, for example, methyl, ethyl, n-propyl, isopropyl, n-propyl Butyl, tert-butyl, n-hexyl or n-decyl. In addition, R _f may be an alkyl group having other substituents on the alkyl group. Specifically, R _f is, for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3- mercaptopropyl or 3-isocyanatopropyl.

When R _f in formula (III-4) represents a C ₂ to C ₁₀ alkenyl group, specifically, R _f is, for example, a vinyl group. In addition, R _f may be an alkenyl group having another substituent on the alkenyl group, and specifically, R _f is, for example, 3-acryloyloxypropyl or 3-methacryloyloxypropyl.

When R _f in formula (III-4) represents a C ₆ to C ₁₅ aryl group, specifically, R _f is, for example, phenyl, tolyl, or naphthyl. In addition, R _f may be an aryl group having other substituents on the aryl group. Specifically, R _f is, for example, p-hydroxyphenyl (o-hydroxyphenyl), 1-(p-hydroxyphenyl)ethyl (1-(p-hydroxyphenyl) ethyl) -(o-hydroxyphenyl)ethyl), 2-(p-hydroxyphenyl)ethyl (2-(o-hydroxyphenyl)ethyl), or 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl ( 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl).

Furthermore, when R _f in formula (III-4) represents an epoxy group-containing alkyl group or an epoxy group-containing alkoxy group, a specific example of R _f is the aforementioned epoxy group-containing polysiloxane ( The epoxy groups contained in b1) will not be repeated here.

In addition, when R _g of formula (III-4) represents a C ₁ to C ₆ alkyl group, specifically, R _g is, for example, methyl, ethyl, n-propyl, isopropyl, or n-butyl. When R _g in formula (III-4) represents a C ₁ to C ₆ acyl group, specifically, R _g is, for example, an acetyl group. When R _g in formula (III-4) represents a C ₆ to C ₁₅ aryl group, specifically, R _g is, for example, a phenyl group.

Specific examples of the silane monomer (b1-1) include 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, 3-(N-allyl-N-glycidyl)amino Propyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, 3-glycidylpropyltriethoxysilane, 3-glycidylpropylmethyldimethoxysilane, 3-glycidyl propyl methyl diethoxy silane, 3-glycidyl propyl dimethyl methoxy silane, 3-glycidyl propyl dimethyl ethoxy silane, 2- Glycidyl ethyl trimethoxysilane, 2-glycidyl ether ethyl triethoxy silane, 2-glycidyl ether ethyl methyl dimethoxy silane, 2-glycidyl ether ethyl methyl Diethoxysilane, 2-glycidyl ethyl dimethyl methoxy silane, 2-glycidyl ethyl dimethyl ethoxy silane, 4-glycidyl butyl trimethoxy silane Silane, 4-glycidyl butyl triethoxy silane, 4-glycidyl butyl methyl dimethoxy silane, 4- glycidyl butyl methyl diethoxy silane, 4-glycidyl ether Butyldimethylmethoxysilane, 4-glycidyl etherylbutyldimethylethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3, 4-Epoxycyclohexyl)ethyltriethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethyl Oxysilane, ((3-ethyl-3-epoxypropanyl)methoxy)propyltrimethoxysilane, ((3-ethyl-3-epoxypropanyl)methoxy)propyltrimethoxy Ethoxysilane, ((3-ethyl-3-epoxypropanyl)methoxy)propylmethyldimethoxysilane or ((3-ethyl-3-epoxypropanyl)methoxy ) propane dimethylmethoxysilane, commercially available products such as DMS-E01, DMS-E12, DMS-E21, EMS-32 (manufactured by JNC), or combinations thereof.

Specific examples of the silane monomer (b1-1) represented by the formula (III-4) preferably include 3-glycidyl propyl trimethoxy silane, 2-glycidyl ethyl trimethoxy silane, 4 -Glycidyl ether-based butyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane , ((3-ethyl-3-epoxypropanyl)methoxy)propyltrimethoxysilane, ((3-ethyl-3-epoxypropanyl)methoxy)propyltriethoxy Silane, DMS-E01, DMS-E12 or a combination of the above.

The silane monomer (b1-1) is used in an amount of 0.6 mol to 1 mol, preferably 0.65 to 1 mol, based on the total amount of the monomers in the second mixture being 1 mol, more preferably 0.65 to 1 mol. Preferably, it is 0.7 to 1 mole.

The second mixture for reacting to generate the epoxy group-containing polysiloxane (b1) preferably further contains other silane monomers (b1-2) represented by the formula (III-5): Si(R _h ) _f (OR _i ) _4-f formula (III-5) In formula (III-5), R _h is hydrogen atom, C ₁ to C ₁₀ alkyl group, C ₂ to C ₁₀ alkenyl group, C ₆ to C 10 An aryl group of C ₁₅ or an alkyl group containing an acid anhydride group; When f is plural, R _h is the same or different; R _i is a hydrogen atom, an alkyl group of C ₁ to C ₆ , an amide group of C ₁ to C ₆ or an aryl group of C ₆ to C ₁₅ ; when 4-f is a plural number, each of R _i is the same or different; and f is an integer of 1 to 3.

When R _h in formula (III-5) represents an alkyl group of C ₁ to C ₁₀ , an alkenyl group of C ₂ to C ₁₀ , an aryl group of C ₆ to C ₁₅ , the specific examples and preferred examples of the aforementioned R _f shown, and will not be repeated here.

式(III-5-1)

式(III-5-2)

式(III-5-3)When R _h in formula (III-5) represents an acid anhydride group-containing alkyl group, the alkyl group is preferably a C ₁ to C ₁₀ alkyl group. Specifically, the alkyl group containing an acid anhydride group is, for example, ethyl succinic anhydride represented by formula (III-5-1), propyl succinic anhydride represented by formula (III-5-2) or formula ( propylglutaric anhydride represented by III-5-3). It is worth mentioning that the acid anhydride group is a group formed by intramolecular dehydration of dicarboxylic acid, wherein the dicarboxylic acid is, for example, succinic acid or glutaric acid.

Formula (III-5-1)

Formula (III-5-2)

Formula (III-5-3)

When R _i in the formula (III-5) represents a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ aryl group, or a C ₆ -C ₁₅ aryl group, specific examples thereof and preferred examples of the aforementioned R _g shown, and will not be repeated here.

The other silane monomer (b1-2) represented by the formula (III-5) may be used alone or in combination, and the other silane monomer (b1-2) represented by the formula (III-5) contains a silicon atom having 1 silicon atom. compound. Compounds having one silicon atom include silane compounds having four hydrolyzable groups, silane compounds having three hydrolyzable groups, silane compounds having two hydrolyzable groups, and silanes having one hydrolyzable group compound, or a combination thereof.

Specific examples of the silane compound having four hydrolyzable groups include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane , tetra-second butoxysilane, or a combination of the above compounds.

Specific examples of silane compounds having three hydrolyzable groups include methyltrimethoxysilane (MTMS for short), methyltriethoxysilane, methyltriisopropoxysilane, methyltrimethoxysilane, and methyltrimethoxysilane. methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyl Tri-n-butoxysilane (ethyltri-n-butoxysilane), n-propyltrimethoxysilane (n-propyltrimethoxysilane), n-propyltriethoxysilane (n-propyltriethoxysilane), n-butyltrimethoxysilane (n-butyltrimethoxysilane) -butyltrimethoxysilane), n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane ( decyltrimethoxysilane), vinyltrimethoxysilane (vinyltrimethoxysilane), vinyltriethoxysilane (vinyltriethoxysilane), 3-acryoyloxypropyltrimethoxysilane (3-acryoyloxypropyltrimethoxysilane), 3-methacryloyloxysilane 3-methylacryloyloxypropyltrimethoxysilane (MPTMS), 3-methylacryloyloxypropyltriethoxysilane (3-methylacryloyloxypropyltriethoxysilane), phenyltrimethoxysilane (PTMS), phenyl trimethoxysilane Ethoxysilane (phenyltriethoxysilane, PTES), p-hydroxyphenyltrimethoxysilane (p-hydroxyphenyltrimethoxysilane), 1-(p-hydroxyphenyl)ethyltrimethoxysilane (1-(p-hydroxyphenyl)ethyltrimethoxy) , 2-(p-hydroxyphenyl)ethyltrimethoxysilane (2-(p-hydroxyph enyl)ethyltrimethoxysilane), 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane (4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane), trifluoromethyltrimethoxysilane (trifluoromethyltrimethoxysilane), trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane (3-aminopropyltrimethoxysilane), 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-(triphenoxysilyl)propylbutyl 3-triphenoxysilyl propyl succinic anhydride, commercial product manufactured by Shin-Etsu Chemical: 3-trimethoxysilyl propyl succinic anhydride (trade name X-12- 967), commercial products manufactured by WACKER: 3-(triethoxysilyl) propyl succinic anhydride (trade name GF-20), 3-(triethoxysilyl) propyl succinic anhydride 3-(trimethoxysilyl) propyl glutaric anhydride (TMSG), 3-(triethoxysilyl) propyl glutaric anhydride, 3 - (triphenoxysilyl) propyl glutaric anhydride (3-(triphenoxysilyl) propyl glutaric anhydride) or a combination of the above compounds.

Specific examples of the silane compound having two hydrolyzable groups include methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl [2-(Perfluoro-n-octyl)ethyl]dimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiacetoxysilane , di-n-butyldimethoxysilane, or a combination of the above compounds.

Specific examples of the silane compound having one hydrolyzable group include methoxydimethylsilane, methoxytrimethylsilane, methoxymethyldiphenylsilane, tri-n-butylethoxysilane, or Combinations of the above compounds.

The other silane monomer (b1-2) of the structure represented by the formula (III-5) is preferably tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane silane, dimethyldimethoxysilane, dimethyldiethoxysilane, or a combination of the above.

Based on the total amount of the monomers in the second mixture being 1 mol, the amount of the silane monomer (b1-2) used is 0 mol to 0.7 mol, preferably 0 to 0.6 mol, more Preferably, it is 0 to 0.5 moles.

The second mixture may further contain a commercially available silane monomer, and specific examples thereof include KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, and X-21-5843 , X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X -22-170D, X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40 -2655A, X-40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250 , X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A , KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (Shin-Etsu Chemical); Glass Resin (GLASS RESIN, Showa Denko); SH804, SH805, SH806A, SH840, SR24 , SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (made by Toray Dow Corning); FZ3711, FZ3722 (made by NUC); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS -S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (made by JNC) ; MS51, MS56 (manufactured by Mitsubishi Chemical); and partial condensates of GR100, GR650, GR908, GR950 (manufactured by Showa Denko).

The epoxy group contained in the epoxy-containing polysiloxane (b1) is, for example, a glycidyl group, a glycidyloxy group, an epoxycyclohexyl group, or a propylene oxide group. base (oxetanyl group). [ Method for producing epoxy group-containing polysiloxane (b1) ]

The polycondensation reaction of the epoxy group-containing polysiloxane compound can be formed by a general method, for example, adding an organic solvent, water, or optionally a catalyst to the above-mentioned silane compound or a mixture thereof, and then using an oil bath, etc. Heating at 50°C to 150°C is performed, and the preferred heating time is 0.5 hours to 120 hours. During heating, the mixed solution can be stirred or placed under reflux conditions.

The above-mentioned organic solvent is not particularly limited, and may be the same as or different from the solvent (C) contained in the liquid crystal aligning agent of the present invention.

Specific examples of the organic solvent include hydrocarbon compounds such as toluene and xylene; methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone, 2-butanone , 2-hexanone and other ketone solvents; ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and other esters Solvents; ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc.; 1-hexanol, 4-methyl 2-pentanol, ethylene glycol mono Methyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, etc. Alcohol solvents; N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl -Amide-based solvents such as 2-imidazolidinone, or a combination of the above organic solvents.

The above-mentioned organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent used is preferably 10 to 1200 parts by weight, more preferably 30 to 1000 parts by weight, based on 100 parts by weight of all the silane compounds.

The hydrolyzable group of all silane compounds is 1 mol, and the amount of water used is preferably 0.5 mol to 2 mol.

The catalyst is not particularly limited, preferably, the catalyst is selected from acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, or a combination thereof.

Specific examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid, polybasic acid anhydride, or a combination thereof.

Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, or a combination thereof.

Specific examples of the organic base include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; Tertiary organic amines such as n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, etc.; quaternary organic amines such as tetramethylammonium hydroxide Amines, etc., or a combination of the above compounds.

The amount of catalyst used varies according to the type, temperature and other reaction conditions, etc., and can be appropriately set. For example, based on 1 mole of all silane compounds, the amount of the catalyst added is 0.01 mole to 5 moles, preferably 0.03 mol to 3 mol, more preferably 0.05 mol to 1 mol.

From the viewpoint of stability, after the completion of the polycondensation reaction, the organic solvent layer fractionated from the reaction solution is preferably washed with water. When this cleaning is performed, it is preferable to perform the cleaning using water containing a small amount of salt, for example, an ammonium nitrate aqueous solution of about 0.2 wt %. Cleaning can be performed until the water layer after cleaning becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate, molecular sieves, etc. as needed, and the organic solvent is removed to obtain the epoxy group-containing. Polysiloxane (b1).

When the polysiloxane (B) does not use the epoxy group-containing polysiloxane (b1) or the used polysiloxane (b1) does not contain an epoxy group, the obtained liquid crystal aligning agent has Poor environmental resistance and poor adhesion.

式(IV-1)

式(IV-2) 當L¹ 為單鍵時，L⁰ 為單鍵； ＊為鍵結處；及 Z為與環氧基反應形成結合基之一價有機基團。The side chain compound (b2) of the present invention comprises the structure shown in formula (IV): E ¹ -L ⁰ -L ¹ -Z formula (IV) In formula (IV), E ¹ is an alkane of C ₁ to C ₃₀ group, C ₃ to C ₁₀ cycloalkyl group substituted or unsubstituted by C ₁ to C ₂₀ alkyl group or alkoxy group, or C ₁₇ to C ₅₁ hydrocarbon group containing steroid skeleton, the E ¹ alkyl group and part of the hydrogen atoms of the alkoxy group is substituted or unsubstituted; L ⁰ is a single bond, *-O-*, *-COO-* or *-OCO-*; L ¹ is a single bond, C ₁ to C ₂₀ alkylidene, phenylene, biphenylene, cyclohexylene, dicyclohexylene or a group represented by the following formula (IV-1) or formula (IV-2):

Formula (IV-1)

Formula (IV-2) When L ¹ is a single bond, L ⁰ is a single bond; * is a bond; and Z is a valent organic group that reacts with an epoxy group to form a binding group.

The linear or branched C ₁ to C ₃₀ alkyl group described by E ¹ in the above formula (IV), for example, can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-methylbutyl, 2,2-dimethylpropyl , n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,3-dimethyl Butyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl, n-heptyl, 5 -Methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl, 4,4-dimethylpentyl, 3,4-dimethylpentyl, 2 ,4-dimethylpentyl, 1,4-dimethylpentyl, 3,3-dimethylpentyl, 2,3-dimethylpentyl, 1,3-dimethylpentyl, 2 ,2-dimethylpentyl, 1,2-dimethylpentyl, 1,1-dimethylpentyl, 2,3,3-trimethylbutyl, 1,3,3-trimethyl Butyl, 1,2,3-trimethylbutyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2- Methylheptyl, 1-methylheptyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl base, n-pentadecyl base, n-hexadecyl base, n-heptadecyl base, n-octadecyl base, n-nineteen base, etc.

The C ₃ to C ₁₀ cycloalkyl group of E ¹ in the above formula (IV), for example, can be cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl Wait. These cycloalkyl groups mentioned above may or may not be substituted with a C ₁ to C ₂₀ alkoxy group. For specific examples of the C ₁ to C ₂₀ alkoxy group, reference may be made to the specific examples given in the description of the above C ₁ to C ₃₀ alkyl group. For specific examples of the aforementioned C ₁ to C ₂₀ alkoxy groups, reference may be made to the specific examples of the alkyl groups exemplified in the above-mentioned description of the C ₁ to C ₃₀ alkyl groups, and the groups obtained by bonding with an oxygen atom. The alkyl group and the alkoxy group mentioned in E ¹ may have at least a part of hydrogen atoms substituted, and the group used to replace the hydrogen atom can be exemplified by a nitrile group, a fluorine atom, a trifluoromethyl group, and the like.

式(S-1)

式(S-2)

式(S-3)The hydrocarbon group containing C ₁₇ to C ₅₁ of the steroid skeleton described in E ¹ in the above formula (IV) can be, for example, a group represented by the following formula (S-1) to formula (S-3), wherein *5 represents the bond between the above group and L ⁰ of formula (IV).

Formula (S-1)

Formula (S-2)

Formula (S-3)

Preferably, E ¹ can be selected from alkyl groups of C ₁ to C ₂₀ , fluoroalkyl groups of C ₁ to C ₂₀ , groups of the above formula (S-1) and groups of the above formula (S-3) a group formed. Z is preferably a carboxyl group. The C ₁ to C ₂₀ alkylene group described in L ¹ in the above formula (IV) can be, for example, one hydrogen atom removed from each of the aforementioned C ₁ to C ₃₀ alkyl groups And get the group.

式(IV-1)

式(IV-2)

式(IV-3)

式(IV-4)

式(IV-5)

式(IV-6)

式(IV-7)

式(IV-8)The compound represented by the above formula (IV) may preferably be the compounds represented by the following formulae (IV-1) to (IV-8).

Formula (IV-1)

Formula (IV-2)

Formula (IV-3)

Formula (IV-4)

Formula (IV-5)

Formula (IV-6)

Formula (IV-7)

Formula (IV-8)

In formulas (IV-1) to (IV-8), u is an integer from 1 to 5, v is an integer from 1 to 18, w is an integer from 1 to 20, k is an integer from 1 to 5, and p is 0 or 1. q is an integer from 1 to 18, r is an integer from 0 to 18, and j is an integer from 1 to 18. s and t are each independently an integer from 0 to 2. However, s and t are not both 0.

Preferably, v of the above formula (IV-1) is an integer from 1 to 18, and more preferably an integer from 1 to 12. In the above formula (IV-2), w is preferably an integer of 5 to 20, and more preferably 10 to 18. In the above formula (IV-3), w is preferably an integer of 1 to 17, and more preferably an integer of 3 to 12. In the above formula (IV-4), w is preferably an integer of 1 to 15, and more preferably an integer of 1 to 8. In the above formula (IV-8), w is preferably an integer of 1 to 15, and more preferably an integer of 1 to 8. In the above formula (IV-5) and formula (IV-6), r is preferably an integer of 0 to 15, and more preferably an integer of 0 to 8. q of the above formula (IV-6) is preferably an integer of 1 to 12, and more preferably an integer of 1 to 5. In the above formula (IV-8), j is preferably an integer of 1 to 15, and more preferably an integer of 1 to 8.

式(IV-1’)

式(IV-2’)

式(IV-3’)

式(IV-4’)

式(IV-5’)

式(IV-6’)

式(IV-7’)

式(IV-8’)Among the above-mentioned compounds, at least one of the above formulae (IV-2) to (IV-5), formula (IV-7) and formula (IV-8) is preferred. Specifically, the following formulae (IV-1') to (IV-8') are preferred.

Formula (IV-1')

Formula (IV-2')

Formula (IV-3')

Formula (IV-4')

Formula (IV-5')

Formula (IV-6')

Formula (IV-7')

Formula (IV-8')

When the polysiloxane (B) does not use the side chain compound (b2), the obtained liquid crystal aligning agent has poor environmental resistance and poor adhesion.

Based on the total amount of the monomers in the second mixture being 1 mol, the side chain compound (b2) is used in an amount of 0.05 mol to 0.5 mol, preferably 0.1 mol to 0.45 mol, and then 0.2 mol Ear to 0.4 mole is better. If the usage-amount of this side chain compound (b2) is in the said range, the environment resistance of the obtained liquid crystal aligning agent will be favorable.

Based on 100 parts by weight of the polymer (A), the amount of polysiloxane (B) used is 1 part by weight to 30 parts by weight, preferably 1 part by weight to 28 parts by weight, and 1 part by weight To 25 parts by weight is more preferable. [ Method for producing polysiloxane (B) ]

The polysiloxane (B) used in the present invention can be synthesized by reacting the above-mentioned epoxy group-containing polysiloxane (b1) with the side chain compound (b2) in the presence of a catalyst.

As the catalyst, a known compound such as an organic salt or a curing accelerator that can promote the reaction between an epoxy compound and an acid anhydride can be used.

The above-mentioned organic salts include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, etc. Tertiary organic amines such as amine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, and quaternary organic amines such as tetramethylammonium hydroxide, etc. Among these organic amines, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine, or tetramethylammonium hydroxide such as tetramethylammonium hydroxide are preferred. grade organic amines.

Specific examples of the above-mentioned hardening accelerators include tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, and triethanolamine; 2-methylamine; Imidazole, 2-n-heptylimidazole, 2-n-alkylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl- 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-(2-cyano Ethyl)-2-5-n-undecylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4- Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-(2-cyanoethyl)-2 -Phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, l-(2-cyanoethyl-2-n-undecylimidazolium trimellitate , 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium trimellitic acid salt, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-S-triazine, 2,4-diamino-6-(2'-n-decyl) Monoalkylimidazolyl)ethyl-S-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-S-triazine , 2-methylimidazole trimeric isocyanate adduct, 2-phenylimidazole trimeric isocyanate adduct, 2,4-diamino-6-[2'-methylimidazolyl- (1')] Imidazole compounds such as trimeric isocyanate adducts of ethyl-S-triazine; organophosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenylphosphite; benzyltriphenyl benzyl triphenyl phosphonium chloride, tetra-n-butyl phosphonium bromide, methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, n-butyl triphenyl phosphonium bromide, tetraphenyl Phosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium-O,O-diethylphosphonium dithiosulfate (tetra-n-butylphosphonium- O,O-diethyl phosphorodithionate), tetra-n-butylphosphonium benzotriazolate (tetra-n-butylphosphonium benzotriazolate), tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenyl Quaternary phosphonium salts such as phosphonium tetraphenyl borate; diazabicycloalkene of 1,8-diazabicyclo[5.4.0]undecene-7 or its organic acid salt; zinc octoate, tin octoate , Organometallic compounds such as aluminum acetylacetone complex; tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylchloride Quaternary ammonium salts such as ammonium chloride; boron compounds such as boron trifluoride and triphenyl borate; metal halogen compounds such as zinc chloride and tin tetrachloride; dicyandiamide or amine and High melting point dispersion type latent hardening accelerators such as amine addition type accelerators such as adducts of epoxy resins; surface hardening accelerators such as the above imidazole compounds, organophosphorus compounds or quaternary phosphonium salts are coated with polymers Microcapsule type latent hardening accelerator; amine salt type latent hardening accelerator; high temperature dissociation type thermal cationic polymerization latent hardening accelerator such as Lewis acid salt, Bronsted acid salt, etc. Latent hardening accelerator, etc.

Specific examples of the hardening accelerator are preferably quaternary ammonium salts including tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.

Specific examples of the hardening accelerator are preferably quaternary ammonium salts including tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.

The reaction temperature is preferably 0°C to 200°C, and more preferably 50°C to 150°C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

The synthesis reaction of the polysiloxane (B) can be carried out in the presence of an organic solvent, if necessary. The organic solvent is not particularly limited, and can be the same as or different from the organic solvent used in the preparation of the epoxy group-containing polysiloxane (b1) and the solvent (C) contained in the liquid crystal alignment agent of the present invention. same. Specific examples of the above organic solvent are preferably 2-butanone, 2-hexanone, methyl isobutyl ketone, n-butyl acetate, or a combination thereof.

The weight average molecular weight of the polysiloxane (B) of the present invention is 2,000 to 20,000; preferably 3,000 to 18,000; more preferably 5,000 to 15,000.

The solvent used in the liquid crystal aligning agent of the present invention is not particularly limited, as long as it can dissolve the polymer (A), polysiloxane (B) and other arbitrary components and does not react with them, preferably The same as the solvent used in the aforementioned synthesis of the polyamic acid, the poor solvent used in the synthesis of the polyamic acid can also be used in combination.

Specific examples of the solvent (C) include, but are not limited to, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol Monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, Ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Or N,N-dimethylformamide or N,N-dimethylacetamide (N,N-dimethyl acetamide). The solvent (C) may be used alone or in combination of two or more.

Based on 100 parts by weight of the polymer (A), the amount of the solvent (C) used is 500 to 3000 parts by weight, preferably 800 to 3000 parts by weight, and more preferably 800 to 2500 parts by weight.

Within the scope of not affecting the efficacy of the present invention, the liquid crystal alignment agent can also optionally add additives (D), wherein the additives (D) include compounds with at least two epoxy groups, silane compounds with functional groups, or a combination thereof.

Compounds with at least two epoxy groups include but are not limited to ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene Glycol Diglycidyl Ether, Neopentyl Glycol Diglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether, Glycerol Diglycidyl Ether, 2,2-Diglycidyl Ether Bromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl- m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4 '-diaminodiphenylmethane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, or a combination of the foregoing.

The compound having at least two epoxy groups may be used alone or in combination.

The compound having at least two epoxy groups may be used in an amount of 0 to 40 parts by weight, and preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the polymer (A).

Specific examples of silane compounds having functional groups include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane, -aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyl Dimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane Silane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine Triamine, 10-trimethoxysilyl-1,4,7-triazdecane, 10-triethoxysilyl-1,4,7-triazdecane, 9-trimethoxysilyl- 3,6-Diaznonyl acetate, 9-triethoxysilyl-3,6-diaznonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl N-phenyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (ethylene oxide)-3-aminopropyltrimethoxysilane, N-bis(ethylene oxide)-3-aminopropyltriethoxysilane, or a combination of the foregoing.

The silane compound having a functional group can be used alone or in combination.

Based on 100 parts by weight of the polymer (A), the silane compound having a functional group may be used in an amount of 0 to 10 parts by weight, and preferably 0.5 to 10 parts by weight.

The additive (D) is preferably used in an amount of 0.5 to 50 parts by weight, and more preferably 1 to 45 parts by weight, based on 100 parts by weight of the polymer (A) in total. [ Manufacturing method of liquid crystal alignment agent ]

The preparation method of the liquid crystal alignment agent of the present invention is not particularly limited, and can be prepared by a general mixing method. For example, firstly, the polymer (A) and polysiloxane (B) prepared in the above manner are mixed uniformly to form a mixture. Next, the solvent (C) is added at a temperature of 0°C to 200°C, and the additive (D) is optionally added, and finally the stirring device is continuously stirred until dissolved. In addition, it is preferable to add the solvent (C) at a temperature of 20°C to 60°C.

At 25° C., the viscosity of the liquid crystal alignment agent of the present invention is usually 15 cps to 35 cps, preferably 17 cps to 33 cps, and more preferably 20 cps to 30 cps. [ Liquid Crystal Alignment Film and Method for Manufacturing Liquid Crystal Display Element ]

The present invention further provides a liquid crystal alignment film, which is formed by the aforementioned liquid crystal alignment agent.

The present invention also provides a liquid crystal display element comprising the aforementioned liquid crystal alignment film.

The liquid crystal alignment film of the present invention is formed using the liquid crystal alignment agent prepared above. Furthermore, the liquid crystal display element of this invention has the liquid crystal aligning film formed from the said liquid crystal aligning agent. The operation mode of the liquid crystal display element is not particularly limited, and it is preferably a vertical alignment type.

The liquid crystal alignment film and the manufacturing method of the liquid crystal display element of the present invention may include: coating the liquid crystal alignment agent of the present invention on the conductive films of a pair of substrates having a conductive film, and then heating the substrates to form a coating film The first step; the second step of arranging the above-mentioned pair of substrates formed with the coating film opposite to each other to construct a liquid crystal cell; and irradiating the liquid crystal cell with light on the pair of substrates with the conductive film under the condition of applying a voltage the third step. [Step 1: Formation of coating film]

In this step, two substrates with patterned transparent conductive films are used as a pair, and the liquid crystal alignment agent of the present invention is respectively coated on the surfaces of the substrates formed with the transparent conductive films. Preferably, a lithographic plate can be used. The coating of the liquid crystal alignment agent is carried out by a printing method, a spin coating printing method, a roll coating method or an ink jet method. The substrate referred to here can be, for example, glass such as float glass and soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether terephthalate, polycarbonate, poly(alicyclic olefin) and other plastic transparent substrates. As the transparent conductive film provided on the surface of the substrate, NESA film (registered trademark of American PPG Corporation) formed of tin oxide (SnO ₂ ), indium oxide and tin oxide (In ₂ O ₃ -SnO ₂ ) can be used. ITO film. The patterned transparent conductive film can be formed by, for example, forming an unpatterned transparent conductive film first, followed by a patterning method of photo-etching, and using a mask with a predetermined pattern during the formation of the transparent conductive film, etc. achieved. When coating the liquid crystal aligning agent, in order to have good adhesion between the substrate surface and the transparent conductive film and the coating film, the surface of the substrate on which the coating film is formed can also be pre-coated with functional silane compounds and functional titanium compounds. Process before waiting.

After the liquid crystal alignment agent is applied, in order to prevent the applied liquid crystal alignment agent from dripping, prebake is preferably performed. The pre-baking temperature can be 30°C to 200°C, preferably 40°C to 150°C, and more preferably 40°C to 100°C. The pre-baking time may be 0.25 minutes to 10 minutes, preferably 0.5 minutes to 5 minutes. After that, the solvent is completely removed, and the above-mentioned substrate is subjected to a step of firing (post-baking) in order to form the necessary thermal imidization of the polymer and the structure of the amide acid. The post-baking temperature may be 80°C to 300°C, preferably 120°C to 250°C. The post-baking time may be 5 minutes to 200 minutes, preferably 10 minutes to 100 minutes. Therefore, the thickness of the formed film may be 0.001 μm to 1 μm, preferably 0.005 μm to 0.5 μm.

The heating step after coating the liquid crystal alignment agent can remove the organic solvent, thus forming the coating film of the liquid crystal alignment film. At this time, the polymer contained in the liquid crystal aligning agent of the present invention includes a polyamic acid, or an imide polymer having an imine structure and an imide structure. After that, the formed coating film is further heated, and the above-mentioned polymer undergoes a dehydration ring-closure reaction to form an imidized coating film. The coating film formed by the above method can be used directly as a liquid crystal alignment film, but can also be subjected to a predetermined rubbing treatment. [Step 2: Construction of Liquid Crystal Cells]

In this step, two substrates on which the above-mentioned liquid crystal alignment films are formed are provided, and a liquid crystal layer containing a liquid crystal compound and a photopolymerizable compound is disposed between the two oppositely arranged substrates to form a liquid crystal cell. As a method of producing a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a known method (vacuum injection method). First, two substrates are placed opposite to each other so that a gap (cell gap) is formed between the oppositely placed liquid crystal alignment films. The periphery of the two substrates is bonded with an adhesive, and the liquid crystal compound and the photopolymerizable compound are injected into the cell gap divided by the surface of the substrate and the adhesive and filled, and then the injection hole is sealed to obtain a liquid crystal. cell.

The second method is called Liquid Crystal Dropping (One Drop Filling; ODF). A predetermined position on the substrate on which one of the two substrates of the liquid crystal alignment film is formed is coated with, for example, an ultraviolet curable adhesive. Next, after dropping the mixture of the liquid crystal compound and the photopolymerizable compound on the predetermined position of the liquid crystal alignment film, the liquid crystal alignment film and the liquid crystal alignment film of the other substrate are placed opposite to each other, and the two substrates are bonded together to make the liquid crystal on the substrate. Then, the entire substrate is irradiated with ultraviolet light to harden the adhesive to manufacture liquid crystal cells. No matter which method is used, after the liquid crystal cell is formed, the substrate is heated to a temperature at which the liquid crystal compound used becomes isotropic, and then slowly cooled to room temperature to remove the flow alignment during liquid crystal filling.

As the above-mentioned adhesive, epoxy resin containing alumina balls as a hardener and a spacer can be used. The liquid crystal compound can preferably be selected from nematic liquid crystals with negative dielectric anisotropy, for example, dicyanophenyl liquid crystals, pyridazine-based liquid crystals, Schiff-based liquid crystals, azo-based liquid crystals, and biphenyl liquid crystals. , phenylcyclohexyl liquid crystal, terphenyl liquid crystal, etc. Furthermore, in order to increase the response speed of the PSA mode liquid crystal display device, it is preferable to use together an alkenyl liquid crystal, which is a monofunctional liquid crystal compound having one alkenyl group or a fluoroalkenyl group. As the alkenyl liquid crystal, conventional alkenyl liquid crystals, such as compounds represented by the following formulae (L1-1) to (L1-9), can be used.

As the photopolymerizable compound, a compound having a functional group capable of radical polymerization, such as an acryl group, a methacryl group, and a vinyl group, can be used. Among them, compounds having at least two functional groups of acryl group and methacryl group are preferably used from the viewpoint of reactivity. In addition, from the viewpoint of maintaining stable alignment of liquid crystal molecules, the photopolymerizable compound is a liquid crystal skeleton, and a compound having at least two of a cyclohexane ring and a benzene ring is preferably used. In addition, a well-known photopolymerizable compound can be used for this photopolymerizable compound. The use amount of the photopolymerizable compound preferably accounts for 0.1% to 0.5% of the total weight of the liquid crystal compound. The thickness of the liquid crystal layer is preferably 1 μm to 5 μm. [Step 3: Exposure Step]

After the liquid crystal cell is constructed, a voltage is applied between the conductive films of the pair of substrates, and light is simultaneously irradiated. The voltage applied here may be, for example, a direct current or alternating current of 5V to 50V. Furthermore, the irradiated light can be, for example, ultraviolet light and visible light including light with a wavelength of 150 nm to 800 nm, but preferably ultraviolet light including light with a wavelength of 300 nm to 400 nm. As a light source for irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. In addition, the light source can be used in combination with filters, diffraction gratings, etc. to obtain ultraviolet light in the above-mentioned preferred wavelength range.

The irradiation amount of light may be 1000 J/m ² or more and less than 100,000 J/m ² , preferably 1000 J/m ² to 50,000 J/m ² . For example, it is known that a light irradiation amount of 100,000 J/m ² is required to manufacture a PSA mode liquid crystal display element. However, the liquid crystal display element of the present invention can utilize an irradiation light amount of less than 100,000 J/m ² or even less than 50,000 J/m ² , a liquid crystal display element with predetermined pretilt angle characteristics is obtained, and the manufacturing cost of the liquid crystal display element is reduced. Furthermore, deterioration of electrical properties and deterioration of reactivity of liquid crystal molecules due to strong light irradiation can also be suppressed.

Then, the polarizing plate is attached to the outer surface of the liquid crystal cell to obtain the liquid crystal display element of the present invention. The above-mentioned polarizing plate can be exemplified by a polarizing film called "H film" which is stretched and aligned with polyvinyl alcohol and absorbs iodine liquid, and a protective film of cellulose acetate sandwiched between the above-mentioned polarizing film. plate.

The liquid crystal display element of the present invention can be applied to various devices, such as: watches, portable game machines, word processors, notebook computers, navigation systems, cameras, PDAs, digital cameras, mobile phones, smart phones, various monitors , LCD TV, electronic signage and other display devices.

The following examples are used to illustrate the present invention in detail, but it is not intended that the present invention is limited to the contents disclosed by these examples. [ Preparation of Polymer (A) ] <Synthesis Example A1-1>

A nitrogen inlet, a stirrer, a condenser and a thermometer were set on a four-necked conical flask with a volume of 500 ml, and nitrogen was introduced. Then, in a four-necked conical flask, add 0.005 mol of a2-1-1 shown in Table 1-1, 0.02 mol of a2-2-1, 0.025 mol of a2-3-2 and 80 grams of N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, abbreviated as NMP), and stirred at room temperature until dissolved. Next, 0.05 mol of a1-1 shown in Table 1 and 20 g of NMP were added, and the mixture was reacted at room temperature for 2 hours. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60° C. to obtain a polymer (A1-1). <Synthesis Examples A1-2 to A1-13 and Comparative Synthesis Examples A1-14 to A1-16>

Synthesis Examples A1-2 to A1-13 and Comparative Synthesis Examples A1-14 to A1-16 were prepared by the same procedures as those of Synthesis Example A1-1, except that the tetracarboxylic dianhydride compound or The types of diamine compounds and their usage amounts are shown in Table 1-1 and Table 1-2. <Synthesis example A2-1>

A nitrogen inlet, a stirrer, a condenser and a thermometer were set on a four-necked conical flask with a volume of 500 ml, and nitrogen was introduced. Then, in a four-necked conical flask, add 0.005 mol of a2-1-1 shown in Table 2-1, 0.02 mol of a2-2-1, 0.025 mol of a2-3-2 and 80 grams of NMP and stirred at room temperature until dissolved. Next, 0.05 mol of a1-1 shown in Table 1 and 20 g of NMP were added. After reacting at room temperature for 6 hours, 97 g of NMP, 0.05 mol of acetic anhydride and 0.1 mol of pyridine were added, the temperature was raised to 120° C., and stirring was continued for 2 hours to carry out imidization reaction. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60° C. to obtain a polymer (A2-1). <Synthesis Examples A2-2 to A2-13 and Comparative Synthesis Examples A2-14 to A2-16>

表1-2：

表2-1：

表2-2：

表1-1、表1-2、表2-1及表2-2中：

[ 製備聚矽氧烷 (B)] ＜合成例B-1＞Synthesis Examples A2-2 to A2-13 and Comparative Synthesis Examples A2-14 to A2-16 were prepared by the same procedure as Synthesis Example A2-1, except that the tetracarboxylic dianhydride compound or The types of diamine compounds and their usage amounts are shown in Table 2-1 and Table 2-2; and the usage amounts of catalysts for dehydrating agent and dehydration ring-closure reaction are changed. Table 1-1:

Table 1-2:

table 2-1:

Table 2-2:

In Table 1-1, Table 1-2, Table 2-1 and Table 2-2:

[ Preparation of polysiloxane (B)] <Synthesis example B-1>

A stirrer, a condenser and a thermometer were set on a three-necked flask with a volume of 500 ml. Then, in a three-necked flask, add 1.00 moles of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (hereinafter referred to as ECETS) and 600 grams of propylene glycol monomethyl ether (hereinafter referred to as PGME), and a triethylamine (Triethylamine, hereinafter referred to as TEA) aqueous solution (20 g TEA/200 g H ₂ O) was added within 30 minutes while stirring at room temperature. Next, the three-necked flask was immersed in an oil bath at 30°C and stirred for 30 minutes, then the oil bath was heated to 90°C within 30 minutes, and when the internal temperature of the solution reached 75°C, the heating and stirring were continued for 6 hours for polycondensation. . After the reaction is completed, the organic layer is taken out and washed with a 0.2 wt% ammonium nitrate aqueous solution to obtain a solution of the epoxy group-containing polysiloxane compound.

Next, 0.50 mol of the ethylenically unsaturated compound b-2-1 and 0.2 g of a hardening accelerator UCAT 18X (manufactured by SAN-APRO) were added to the solution of the epoxy group-containing polysiloxane compound. Then, the three-necked flask was immersed in a 30°C oil bath and stirred for 10 minutes, then the oil bath was heated to 115°C within 30 minutes, and when the internal temperature of the solution reached 100°C, heating and stirring were continued for 24 hours. After the reaction is completed, the organic layer is taken out, washed with water, dried with magnesium sulfate, and the solvent is removed to obtain polysiloxane (B-1). <Synthesis Example B-2 to Synthesis Example B-8 and Comparative Synthesis Example B'-1 to Comparative Synthesis Example B'-3>

表3-2：

表3-1、表3-2中：

[ 液晶配向劑、液晶配向膜及液晶顯示元件之製備 ] ＜實施例1＞Synthesis Example B-2 to Synthesis Example B-8 and Comparative Synthesis Example B'-1 to Comparative Synthesis Example B'-3 are the same steps as those of Synthesis Example B-1 to prepare the photoreactive group-containing polysiloxane alkane, and the difference lies in: changing the type of polysiloxane (B) reactant and its usage, the type of catalyst and solvent and its usage, reaction temperature and polycondensation time (as shown in Table 3-1, shown in Table 3-2). Table 3-1:

Table 3-2:

In Table 3-1 and Table 3-2:

[ Preparation of Liquid Crystal Alignment Agent, Liquid Crystal Alignment Film, and Liquid Crystal Display Device ] <Example 1>

100 parts by weight of polymer (A1-1), 1 part by weight of polysiloxane (B-1), and 500 parts by weight of N-methyl-2-pyrrolidone (C-1 for short) were weighed, and placed in a room The liquid crystal aligning agent of Example 1 can be formed by continuously stirring with a stirring device until it is dissolved under the temperature.

The liquid crystal aligning agent was evaluated for each test item, and the results obtained are shown in Table 4. <Examples 2 to 39 and Comparative Examples 1 to 12>

表4-2：

表4-3：

表5：

表4-1、表4-2、表4-3及表5中：

[ 評價方式 ] ＜ 醯亞胺化率 ＞ Examples 2 to 39 and Comparative Examples 1 to 12 are to prepare the liquid crystal alignment agent in the same steps as in Example 1, except that the types and amounts of polymer compositions, solvents and additives are changed, as shown in the table. 4-1, Table 4-2, Table 4-3 and Table 5. These liquid crystal aligning agents were evaluated for each test item, and the results obtained are shown in Table 4-1, Table 4-2, Table 4-3, and Table 5. Table 4-1:

Table 4-2:

Table 4-3:

table 5:

In Table 4-1, Table 4-2, Table 4-3 and Table 5:

[ Evaluation method ] < Imidization rate >

The imidization rate refers to the ratio of the number of imine rings through the total amount of the number of imide functional groups and the number of imine rings in the polymer, expressed as a percentage.

Δ1：NH基質子在10ppm附近的化學位移(chemical shift)所產 生的峰值(peak)面積； Δ2：其他質子的峰值面積； α：聚合物組成物的前驅物(聚醯胺酸)中的NH基的1個質子相對於其他質子的個數比例。＜ 耐環境性 ＞ The detection method is to separate the polymer compositions of the synthesis examples after drying under reduced pressure, and then dissolving them in a suitable deuteration solvent, for example: deuterated dimethyl sulfite, using tetramethylsilane as the reference material. , the 1H-nuclear magnetic resonance ^{(1H-Nuclear magnetic resonance, 1 H} -NMR) results are measured at room temperature (eg, 25°C), and the imidization rate (%) can be obtained from the following formula.

Δ1: The peak area generated by the chemical shift of the NH proton around 10 ppm; Δ2: The peak area of other protons; α: The NH in the precursor (polyamide) of the polymer composition The ratio of the number of one proton to other protons in the base. ＜ Environmental resistance ＞

Using the liquid crystal alignment agents of Example 1 to Example 39 and Comparative Example 1 to Comparative Example 12, a liquid crystal display element was fabricated according to the above method, and the prepared liquid crystal display element was placed at a temperature of 65° C. and a relative humidity of 85%. In the same environment, after 120 hours, the ion densities were measured using an electrical measuring machine (manufactured by Toyo Corporation, Model 6254). The test conditions are to apply a 1.7V voltage and a 0.01Hz triangular wave at a temperature of 60°C. In the current-voltage waveform, the ion density (pC) can be measured by calculating the peak area in the range of 0 to 1V, and the measurement area is 3cm × 4cm . The lower the ion density, the better the environmental resistance. The evaluation criteria of the ion density are as follows. ◎: Ion density < 20 pC ○: 20 pC ≦ Ion density < 40 pC △: 40 pC ≦ Ion density < 50 pC ╳: 50 pC ≦ Ion density < Adhesion >

The above-mentioned liquid crystal alignment agent was spin-coated on the glass substrate, and then pre-baked at a temperature of 80°C using a heating plate. Heating at a temperature of 80° C. for 1 hour (post-baking) was continued in a nitrogen-exchanged oven to form a coating film with an average film thickness of 0.08 μm. The same steps as above were repeated to prepare two glass substrates with coating films. Take one of the glass substrates with a coating film, apply an ODF sealant (S-WB42, manufactured by Sekisui Chemicals) with a diameter of about 5 mm on the coating film, and contact the ODF sealant with the coating film of the other glass substrate. The two glass substrates are bonded together. Then, it was irradiated with a metal halide lamp at 100,000 J/m ² (converted at 365 nm), and then heated in an oven at 120° C. for 1 hour. Then, the adhesive force was measured by a tensile and compressive tester (model: SDWS-0201-100SL) of Imada Manufacturing Co., Ltd. to evaluate the adhesiveness of the coating film. The evaluation criteria are as follows: ◎: Adhesion force≧300 gf/mm ² ○ : 300 gf/mm ² > Adhesion ≧ 200 gf/mm ² △: 200 gf/mm ² > Adhesion ≧ 100 gf/mm ² ╳: Adhesion < 100 gf/mm ² .

The above-mentioned embodiments are only to illustrate the principle and effect of the present invention, but not to limit the present invention. Modifications and changes made to the above embodiments by those skilled in the art still do not violate the spirit of the present invention. The scope of the rights of the present invention should be listed in the scope of the patent application described later.

Claims (16)

A liquid crystal alignment agent, comprising: a polymer (A) prepared by reacting a first mixture comprising a tetracarboxylic dianhydride component (a1) and a diamine component (a2), and the polymer (A) ) is selected from the group consisting of polyimide polymers, polyimide polymers, polyimide-based block copolymers or any combination of the foregoing polymers; polysiloxane (B); and solvent (C); Wherein the diamine component (a2) includes at least one first diamine compound (a2-1) represented by formula (1): H ₂ NR _a -NH ₂ formula (1) In formula (1), R _a is Divalent units represented by formula (1-1) to formula (1-11):

In formula (1-1) to formula (1-11), * is a bond; the polysiloxane (B) includes an epoxy group-containing polysiloxane (b1) and a side chain compound (b2) The epoxy group-containing polysiloxane (b1) comprises a copolymer obtained by hydrolysis and partial condensation of a second mixture; the second mixture comprises formula (III-4) Silane monomer shown (b1-1): Si(R _f ) _b (OR _g ) _4-b Formula (III-4) In formula (III-4), R _f is a hydrogen atom, C ₁ to C ₁₀ alkyl, C ₂ to C ₁₀ alkenyl, C ₆ to C ₁₅ aryl, epoxy-containing alkyl or epoxy-containing alkoxy, and at least one R _f is an epoxy-containing An alkyl group or an alkoxy group containing an epoxy group; when b is plural, R _f is the same or different; R _g is a hydrogen atom, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ aryl group or C ₆ to C ₁₅ aryl; when 4-b is plural, each R _g is the same or different; and b is an integer of 1 to 3; the side chain compound (b2) comprises a compound represented by formula (IV) Structure: E ¹ -L ⁰ -L ¹ -Z (IV) In formula (IV), E ¹ is an alkyl group of C ₁ to C ₃₀ , substituted by an alkyl group of C ₁ to C ₂₀ or an alkoxy group or not Substituted C ₃ to C ₁₀ cycloalkyl group, or C ₁₇ to C ₅₁ hydrocarbon group containing steroid skeleton, part of hydrogen atoms of the E ¹ alkyl group and alkoxy group is substituted or unsubstituted; L ⁰ is a single bond, *-O-*, *-COO-* or *-OCO-*; L ¹ is a single bond, C ₁ to C ₂₀ alkylene, phenylene, biphenylene, cyclohexylene, two Cyclohexylene or a group represented by the following formula (IV-1) or formula (IV-2):

When L ¹ is a single bond, L ⁰ is a single bond; * is a bond; and Z is a valent organic group that reacts with an epoxy group to form a binding group. The liquid crystal aligning agent according to claim 1, wherein the epoxy group-containing polysiloxane (b1) comprises a group represented by formula (III-1), a group represented by formula (III-2), and a group represented by formula (III) -3) At least one of the bases represented by:

In formula (III-1), B is an oxygen atom or a single bond; c is an integer of 1 to 3; and d is an integer of 0 to 6; when d is 0, B is a single bond;

In formula (III-2), e is an integer from 0 to 6;

In formula (III-3), D is a C ₂ to C ₆ alkylene group; and E is a hydrogen atom or a C ₁ to C ₆ alkyl group. The liquid crystal alignment agent according to claim 1, wherein the diamine component (a2) further comprises a second diamine compound (a2-2) represented by the formula (2):

In formula (2), R ¹⁵ is selected from -O-,

,

,

,

and

and R ¹⁶ is an organic group represented by formula (2-1):

In formula (2-1): R ¹⁷ is hydrogen, fluorine or methyl; R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a single bond, -O-,

,

,

,

,

or C ₁ to C ₃ alkylene; R ²¹ is selected from

and

The group consisting of; wherein: R ²³ and R ²⁴ independently represent hydrogen, fluorine or methyl; R ²² is selected from hydrogen, fluorine, C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ fluoroalkyl , C ₁ to C ₁₂ alkoxy group, -OCH ₂ F, -OCHF ₂ and -OCF ₃ ; a represents an integer of 1 or 2; g, m and i each independently represent an integer of 0 to 4 ; y, h and x each independently represent an integer from 0 to 3, and y+h+x≧3; and z1 and z2 each independently represent 1 or 2; when R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , When there are more than one R ²¹ , R ²³ or R ²⁴ , they are the same or different from each other. The liquid crystal alignment agent according to claim 1, wherein the diamine component (a2) further comprises a third diamine compound (a2-3) represented by the formula (3):

In formula (3), X is an organic group containing a C ₆ to C ₃₀ aromatic ring; and n is an integer of 1 to 4. According to the liquid crystal alignment agent of claim 4, the third diamine compound (a2-3) is selected from the group consisting of formula (3-1) to formula (3-5):

In formula (3-1) to formula (3-5), X ₁ and X ₃ independently represent a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-; X ₂ represents a straight chain alkyl group of C ₁ to C ₅ or a branched chain alkyl group of C ₁ to C ₅ ; n1 and n7 independently represent integers of 1 to 4; n2 and n3 independently represent integers of 0 to 4, and n2+n3 are integers of 1 to 4; and n4, n5 and n6 independently represent integers of 1 to 5. The liquid crystal aligning agent according to claim 1, wherein based on the total usage amount of the diamine component (a2) is 100 mol, the usage amount of the first diamine compound (a2-1) represented by the formula (1) 3 to 60 moles. The liquid crystal aligning agent according to claim 3, wherein, based on the total usage amount of the diamine component (a2) is 100 moles, the use of the second diamine compound (a2-2) represented by the formula (2) The amount is 5 to 60 moles. The liquid crystal aligning agent according to claim 4, wherein, based on the total usage amount of the diamine component (a2) is 100 moles, the use of the third diamine compound (a2-3) represented by the formula (3) The amount is 3 to 97 moles. The liquid crystal alignment agent according to claim 1, wherein, based on the total amount of monomers in the second mixture being 1 mol, the amount of the silane monomer (b1-1) used is 0.6 mol to 1 mol. The liquid crystal aligning agent according to claim 1, wherein the side chain compound (b2) is used in an amount of 0.05 mol to 0.5 mol based on the total amount of monomers in the second mixture being 1 mol. The liquid crystal alignment agent according to claim 1, wherein, based on 100 parts by weight of the polymer (A), the amount of the polysiloxane (B) used is 1 to 30 parts by weight, and the solvent ( C) is used in an amount of 500 to 3000 parts by weight. The liquid crystal alignment agent according to claim 1, wherein the polymer (A) is a combination of a polyimide polymer (A1) and a polyimide polymer (A2). The liquid crystal alignment agent according to claim 12, wherein, based on 100 parts by weight of the polymer (A), the amount of the polyamide polymer (A1) used is 20 to 60 parts by weight, and the The polyimide polymer (A2) is used in an amount of 40 to 80 parts by weight. The liquid crystal alignment agent according to claim 1, wherein the imidization rate of the polymer (A) is 30% to 80%. A liquid crystal alignment film formed from the liquid crystal alignment agent according to any one of claims 1 to 14. A liquid crystal display element comprising the liquid crystal alignment film of claim 15.